Process for dyeing or printing fibrous materials of aromatic polyesters



BROCESS 1FOR- DYEING OR Claims priority,

.4rpheny1am o-a.n raquinon .fre rt United, States Patent Office Patented 'Apr.2,-1963 ;This :inyention; is based on: the observation that-.yaluable dyeings and prints are produced on fibrous materials of aromatic polyesters, especially polyethylene terephff a 1,-,arnino-Z-cyano-4- yl m especially earn n -Howe s k w lramino Z-cyano 4cyc1oalkylaminoor l-aminor2 cyano- .partingsoluhili-ty in water. ,Ihe ern'rlower falkyLmeans alkyl having at most ,6,carbon,atorns h d e fi ay bes bs it t d the al yl en-phenyl radis l .o e e in the alkyl radical by a eyanogroup andinthe phenyl .radic w ha g n;- at m, g tanal talk o h dr group.

.As :examplespflsuch dye tuff ther .;-may bem i lramino52 cyano4-methylamino l -amino 2-cyano-4-ethylamino lraminoJpyanoA-cyanethylamino -1 amino 2-cyano 4-isopropyl amino 1-amino-2-cyano-4-butylamino-, 1-amino-2-cyano-4-cyclohexylamino-, 1-amino 2-cyano4-phenylamino,

-l-amino-2-cyano-4 p araor =meta methylpheny1) -amino, 1l amino-2-cyano-4-(para-methoxyphenyl) amino-,

:-l arriino-2 cyano-4-(ortho-, metaor para-chlorophenyl) amino-or -I arnino-LcyanoA-(ortho, -metaor .pa-ra-hydroxypheniyl)-am ino-anthraquinone.

, These compounds can be obtaineddn .known,manner by 3 heating the appropriate 1-amino-4-alkylamino-, l-amino- -4-cycl oalkylarninoor l amino-4-phenylamino-anthraquinone-Z-sulfonic acid in water with an alkali metal cyanide.

,I nstead of a single dyestuff there maybe used a mixture of such dyestuffs, :and-=in-this way the aifinity is-often considerably enhanced. There may be used a mixture of different dyestuffs of the kind defined above or a mixture of such a dyestutf with another dyestufi of similar structure, for example, 1:5-dihydroxy-4-nitro-8- or -1:8-dihydroxy-4-nitro-5-phenylami-no-anthraquinone.

For dyeing the aforesaid dyestuffs are advantageously used in a finely dispersed form and in the presence of a dispersing agent, such as a soap, sulfite cellulose waste liquor or a synthetic detergent, or a mixture of a wetting agent and dispersing agent. It is generally of advantage before dyeing to convert the dyestuff into a dyestuif preparation which contains a dispersing agent and the finely divided dyestulf in a form such that a fine dispersion is obtained when the dyestufi preparation is diluted with water. Such dyestuff preparations can be made in known manner, for example, by reprecipitating the dyestuff from sulfuric acid and grinding the suspension so obtained with sulfite cellulose waste liquor, and, if desired, by grinding the dyestutf in a highly efiicient grinding apparatus in the dry or wet state in the presence or absence of :a dispersing agent.

"Raymond :Defago, I

In, order to produce strong dyeingson polyethylene terephthalatefibers it.is..o advantage .toincorporate a swelling agent in the dyebath, orto carry out the dyeing .process under.pressureata.EIIIPfiIfitDIQJbW for example, within theirange.v of 1:20to 140 C. As swelling agents there may be used aromaticcarboxylic acids, forexamplebenzoic acid or salicylic acid-or phenol-s, forexample, orthoor para-hydroxy diphenyl, or aromatic halogen-compounds, for example, cchlorobenzene, ortho-dichlorobenzene or trichlorobenzene, or phenyl methyl earbinol. or diphenyl. The dyeings so obtained are distinguished by their good fastness to sublimation and light.

The -followingexamples illustrate 'the invention, the partsand percentages being by weight.

Example 1 v :-1 part of;an aqueous paste of the dyestutf of the formula II 0 NH- ,and approximately-one part ofbdried sulfite cellulose The material isthen transferred to a dyebath containing 3000-parts of'water inwhich the dyestuff pasteobtained -as described above hasbeen dispersed with the. aid of 4 parts. of the sodiumsalt of N benzyl-n-heptadecyl-benzirn- 'idazol-disulfonic acid. The wholeis heated in apressure vessel to C. andmaintained at thattemperature -for abouthalfan-hour. The materialisthen rinsed well,

and, if necessary, washediforhalf an hour at 60 to- 80 C. with a solution which contains, in 1000 partsof water one part of the sodium salt of N-benzyl- -heptadecylbenzimi'dazol-disulfonic acid. There is obtained a strong greenish-blue dyeing having good properties of fastness. This dyestulr' has a surprisingly good afiinity for polyester fibers, in view of the fact that it has been disclosed by Salvin (American Dyestuif Reporter, 48th year (13.7.59), page 35), that this dyestuff is unsuitable for dyeing cellulose acetate silk on account of its insufficient affinity and insufficient stability in the dyebath and also owing to its slow speed of absorption.

By using, instead of l-amino-2-cyano-4-pheny1aminoanthraquinone, l-amino 2 cyano 4 cyclohexy-larninoanthraquinone there is obtained a somewhat less greenishblue dyeing having the same good properties of fastness.

The good affinity of this dyestuff for polyester fibers is surprising because it must be concluded from Example 6 of the German Patent No. 580,012 to LG. Farbenin'dustr-ie A.G., issued July 4, 1933, that it hardly dyed cellulose acetate silk at all.

The dyestuffs mentioned in the first and third para- Examples 2l0 In the following table are mentioned further dyestuffs which dye polyethylene terephthalate fibers by the process described in Example 1 the tints given in column II.

The above mentioned dyestuffs can also be made by the process of British Patent No. 359,850, to LG. Farbenindustrie A.G., accepted October 29, 1931, by heating the sodium salt of the appropriate 1-amino-4-alkylaminoor l-amino-4phenylamino-anthraquinone 2 sulfonic acid with potassium cyanide in water.

Example 11 100 parts of a fibrous material of polyethylene terephthalate are cleaned for half an hour in a bath containing in 1000 parts of water 1 to 2 parts of the sodium salt of N-benzyl [.L heptadecyl-benzimidazol-disulfonic acid and 1 part of a concentrated aqueous solution of ammonia. The material is then treated in a bath which contains in 1000 parts of water 3 to 5 parts of diammonium phosphate and 0.5 to 1 part of N-benzyl-,uheptadecylbenzimidazol-disulfonic'acid for to minutes at 50 C. There are then added 3 to 5 parts of the sodium salt of ortho-phenylphenol dissolved in 1000 parts of water, and the liquor is maintained at 50 to 55 C. for 15 minutes while circulating the liquor. A dyestutf paste obtained as described in the first paragraph of Example 1 is added and the bath is brought to the boil in the course of half an hour and dyeing is carried on for l to 1 /2 hours at the boil, and the material is then rinsed while warm. A greenish-blue dyeing having good properties of fastness is obtained.

cyano 4 lower alkylaminoanthraquinones,

4. Example 12 The following ingredients are mixed together:

300 parts of gum arabic 1:1) 300 parts of crystal gum (1:2) 250 parts of water 40 parts of cyclohexanone 40 parts of thiodiglycol 50 parts of a solution of strength of the sodium salt of meta-nitrobenzene sulfonic acid 20 parts of a mixture of potassium oleate and pine-oil 1000 parts Into 800 parts of the above stock thickening are stirred by means of a high speed stirring device 200 parts of the dyestutf obtained as described in the first paragraph of Example 1, the stirring being continued until the dyestufi is completely dispersed. A fabric is printed with the resulting printing paste, and the print is dried and steamed for 45 minutes under a pressure of of an atmosphere (gauge). The material is then rinsed for 10 minutes in cold water, centrifuged and dried. There is obtained a fast blue print.

What is claimed is: i

l. Polyethylene terephthalate fibers dyed with a dyestufi selected from the group consisting of 1-amino-2- l-amino-Z- cyano-4-cycloalkylaminoanthraquinones and 1-amino-2- cyano-4-phenylaminoanthraquinones free from acid groups imparting solubilityin Water.

2. Polyethylene terephthalate fibers dyed with l-amino- 2-cyano-4-cyclohexylamino-anthraquinone.

3. Polyethylene terephthalate fibers dyed with l-amino- 2-cyano-4-phenylaminoanthraquinone.

4. Polyethylene terephthalate fibers dyed with l-amino- 2-cyano-4-(p-ethoxy-phenyl)-aminoanthraquinone;

5. Polyethylene terephthalate fibers dyed with l-amino- 2-cyano-4-isopropylaminoanthraquinone.

6. Polyethylene terephthalate fibers dyed with l-amino- 2-cyano-4-butylaminoanthraquinone.

References Cited in the file of this patent UNITED STATES PATENTS 1,938,029 Kugel Dec. 5, 1933 2,496,414 Seymour et al Feb. 7, 1950 2,881,045 Mecco et al. Apr. '7, 1959 2,922,691 Grossman Jan. 26, 1960 2,926,987 Freyermuth et al. Mar. 1, 1960 2,937,190 Straley et al May 17, 1960 3,005,822 Jenny Oct. 24, 1961 FOREIGN PATENTS 359,850 Great Britain Oct. 29, 1931 

1. POLYETHYLENE TERPHATHALATE FIBERS DYED WITH A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF 1-AMINO-2CYANO-4-LOWER-ALKYLAMINOANTHRAQUINONES, 1-AMINO-2CYANO-4-CYCLOALKYLAMINOATHRAQUINONES AND 1-AMINO-2CYANO-4-PHENYLAMINOANTHRAQUINONES FREE FROM ACID GROUPS IMPARTING SOLUBILITY IN WATER. 